EP0990059B1 - Niedrig temperatur cvd-verfahren zur herstellung von wismuth enthaltenden dünnen keramik-schichten zur verwendung in ferroelektrischen speicheranordnungen - Google Patents

Niedrig temperatur cvd-verfahren zur herstellung von wismuth enthaltenden dünnen keramik-schichten zur verwendung in ferroelektrischen speicheranordnungen Download PDF

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EP0990059B1
EP0990059B1 EP98934193A EP98934193A EP0990059B1 EP 0990059 B1 EP0990059 B1 EP 0990059B1 EP 98934193 A EP98934193 A EP 98934193A EP 98934193 A EP98934193 A EP 98934193A EP 0990059 B1 EP0990059 B1 EP 0990059B1
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bismuth
precursor
process according
cvd process
film
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EP0990059A1 (de
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Frank S. Hintermaier
Christine Dehm
Wolfgang Hoenlein
Peter C. Van Buskirk
Jeffrey F. Roeder
Bryan C. Hendrix
Thomas H. Baum
Debra A. Desrochers
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Infineon Technologies AG
Advanced Technology Materials Inc
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Advanced Technology Materials Inc
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02197—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides the material having a perovskite structure, e.g. BaTiO3
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31691—Inorganic layers composed of oxides or glassy oxides or oxide based glass with perovskite structure

Definitions

  • the present invention relates to a chemical vapor deposition process for forming bismuth-containing material films on a substrate for applications such as the manufacture of ferroelectric memory devices.
  • ferroelectric materials have been the focus of widespread interest as components of non-volatile memory devices.
  • Non-volatile ferroelectric memory devices function by storage of information through the polarization of a thin ferroelectric material layer reposed between two plates of a capacitor structure. Each such ferroelectric capacitor is connected to a transistor to form a storage cell, in which the transistor controls the access of the read-out electronics to the capacitor. The transistor therefore is connected to bit-line and word-line elements, to constitute the storage cell.
  • the ferroelectric material may be utilized in a stacked capacitor structure which overlies the top of the transistor.
  • the transistor drain e.g., of a MOSFET structure
  • the plug formed of suitable materials such as polysilicon or tungsten.
  • Ferroelectric memories in contrast to dynamic random access memories (DRAMs), have the advantages of retaining stored information in the event of termination of the power supply, and do not require refresh cycles.
  • ferroelectric materials desirably have the following electrical properties: (1) a low coercive field characteristic, facilitating use of a low voltage power supply; (2) a high remnant polarization characteristic, ensuring highly reliable information storage; (3) absence of significant fatigue or life-time deterioration characteristics; (4) absence of any imprint which would alter the stored information (e.g., leading to a preference of a certain polarization such as a logical "1" over a logical "0" character) or otherwise impair the ability to "read” the stored information; and (5) extended retention time, for reliable data storage over an extended period of time.
  • sol-gel methodology permits only a low integration density to be achieved.
  • Some improvement in the sol-gel methodology may be gained by mist or electrospray methods, permitting fabrication of memories up to 4 megabit in capacity.
  • CVD chemical vapor deposition
  • it is necessary to utilize chemical vapor deposition (CVD) processes since CVD affords better conformality and step coverage than layers produced by any other deposition method.
  • CVD process yields deposited films having a high film uniformity, high film density, and the capability to grow very thin films at high throughput and low cost.
  • U.S. Patent 5,527,567 to Desu et al. discloses CVD of a ferroelectric layered structure in a single-step or a two-step process at temperatures which in the single-step process may be in the range of 450-600°C, and in the two-step process may be in the range of 550-700°C in the first step and 600-700°C in the second step.
  • the Desu et al. patent describes post-deposition treatment steps including annealing, deposition of a top electrode, and further annealing.
  • Desu et al. describe as suitable precursors for the respective bismuth, strontium and tantalum components of the SBT film triphenyl bismuth, strontium bis(2,2,6,6-tetramethylheptane-2,5-dionate)tetraglyme adduct and tantalum pentaethoxide, with such precursors being utilized in a solvent medium such as an 8:2:1 mixture of tetrahydrofuran, isopropanol and tetraglyme.
  • a solvent medium such as an 8:2:1 mixture of tetrahydrofuran, isopropanol and tetraglyme.
  • the Desu et al patent mentions Bi(thd) 3 .
  • Desu et al patent describes vaporization at temperatures of 60-300°C.
  • Desu et al. teach evaporation of the precursors in a vaporizer by direct liquid injection, at a temperature in the range of 250-320°C, followed by growth of films from the vaporized precursor at a temperature in the range of 450-800°C on a Pt/Ti/SiO 2 /Si or sapphire substrate, with post-deposition annealing at 750°C.
  • U.S. Patent 5,648,114 describes a method of fabricating an electronic device including CVD deposition of a layered superlattice material which is post-treated to improve its properties.
  • bismuth oxide materials e.g., SrBi 2 Ta 2 O 9 , Bi 4 Ti 3 O 12 , etc.
  • the present invention relates to an improved chemical vapor deposition process for forming bismuth-containing films on substrates for applications such as ferroelectric memory devices.
  • the present invention relates to a process for depositing bismuth or bismuth oxide on a substrate by chemical vapor deposition from a precursor which is vaporized to form a precursor vapor which is then contacted with the substrate.
  • the precursor for depositing the bismuth-containing material is a bismuth ⁇ -diketonate.
  • the precursor for forming the bismuth-containing material on the substrate comprises an anhydrous mononuclear bismuth ⁇ -diketonate, a new material.
  • anhydrous mononuclear bismuth ⁇ -diketonate is preferred, the process of the invention may be broadly practiced with other bismuth ⁇ -diketonates.
  • the bismuth precursor preferably comprises an anhydrous mononuclear bismuth ⁇ -diketonate.
  • the ⁇ -diketonate ligand of the anhydrous mononuclear tris( ⁇ -diketonate) bismuth composition may be of any suitable type, including the illustrative ⁇ -diketonate ligand species set out in Table I below: Table I Beta-diketonate ligand Abbreviation 2,2,6,6-tetramethyl-3,5-heptanedionato thd 1,1,1-trifluoro-2,4-pentanedionato tfac 1,1,1,5,5,5-hexafluoro-2,4-pentanedionato hfac 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato fod 2,2,7-trimethyl-3,5-octanedionato tod 1,1,1,5,5,6,6,7,7,7-decafluoro-2,4-heptaned
  • the use of the anhydrous mononuclear bismuth source material provides improved thermal transport and flash vaporization, leading to a low temperature deposition process of bismuth-containing films of significantly improved stoichiometry, morphology and ferroelectric character, in relation to bismuth-containing films formed by the triphenylbismuth precursor conventionally employed by the prior art.
  • the mononuclear bismuth source material is highly preferred in the practice of the present invention, the invention also contemplates the use of binuclear bismuth precursors, as well as mixtures of mononuclear and binuclear bismuth source materials.
  • the present invention relates to a method of forming an SBT film on a substrate by chemical vapor deposition from precursors for the strontium, bismuth and tantalum constituents, wherein the bismuth precursor comprises a bismuth tris ( ⁇ -diketonate) complex, preferably an anhydrous mononuclear bismuth ⁇ -diketonate.
  • the bismuth precursor comprises a bismuth tris ( ⁇ -diketonate) complex, preferably an anhydrous mononuclear bismuth ⁇ -diketonate.
  • strontium and tantalum precursors may be of any suitable precursor types as source materials for such metal components, but strontium (2,2,6,6-tetramethyl-3,5-heptanedionato) 2 (L), wherein the ligand L is tetraglyme or pentamethyldiethylenetriamine, is a preferred Sr precursor, and the tantalum precursor most preferably comprises Ta(OiPr) 4 (2,2,6,6-tetramethyl-3,5-heptanedionate).
  • the above-discussed SBT precursors may be mixed with any suitable solvent medium, e.g., an 8:2:1 mixture of tetrahydrofuran/isopropanol/tetraglyme, or, more preferably, a 5:4:1 ratio mixture of octane, decane and pentamethyldiethylenetriamine, with the respective Sr, Bi and Ta precursors being individually stored (in solution) in separate reservoirs or supply vessels.
  • any suitable solvent medium e.g., an 8:2:1 mixture of tetrahydrofuran/isopropanol/tetraglyme, or, more preferably, a 5:4:1 ratio mixture of octane, decane and pentamethyldiethylenetriamine, with the respective Sr, Bi and Ta precursors being individually stored (in solution) in separate reservoirs or supply vessels.
  • the three precursor solutions Prior to delivery, the three precursor solutions may be mixed in a liquid delivery system such as that disclosed in U.S. Patent 5,204,314 issued April 20, 1993 in the names of Peter S. Kirlin, et al.
  • the resulting precursor liquid mixture then may be vaporized at suitable temperature in the range of for example 150-240°C, optionally with argon or other carrier gas to transport the resulting multicomponent precursor vapor to the CVD reactor for contacting with the hot substrate.
  • the carrier gas may be mixed with or initially contain oxygen or other oxidant gas.
  • the precursor vapor in the CVD reactor is contacted with the substrate, as for example a Pt/Ti/SiO 2 /Si wafer at a temperature which for example may be on the order of 300-450°C, for sufficient time to permit film growth to occur to the desired extent.
  • the SBT film formed by such method may be an amorphous film or an oriented fluorite-containing film (fluorite usually being oriented, but not always highly), or a combination of the two forms.
  • the amorphous film when present can be transformed to a fluorite structure which can then be transformed to the desired Aurivillius phase by a post-deposition anneal process.
  • the amorphous film may be post-treated to convert same directly to the Aurivillius phase.
  • the annealing temperatures usefully employed to transform an SBT film deposited from a bismuth ⁇ -diketonate precursor into a ferroelectric Aurivillius phase are in the range of about 600 to about 820°C.
  • the solvent mixture of 8:2:1 tetrahydrofuran/isopropanol/tetraglyme described above is illustrative, and other solvent mixtures may be employed.
  • a particularly preferred solvent mixture for the precursors is a 5:4:1 octane/decane/pentamethyldiethylenetriamine mixture.
  • ferroelectric SBT films and device structures on a substrate While the method of the invention is primarily addressed herein in relation to formation of ferroelectric SBT films and device structures on a substrate, the invention is also generally applicable to the formation of other ferroelectric films, including bismuth-containing strontium-based materials, bismuth-containing titanium-based materials and other bismuth-containing film materials including other metallic and oxide components.
  • the present invention is based on the discovery that bismuth ⁇ -diketonates, such as anhydrous mononuclear tris( ⁇ -diketonate) bismuth compositions, may be usefully employed to carry out relatively low temperature chemical vapor deposition of bismuth-containing films, such as bismuth-containing ferroelectric, semiconductor and superconducting films, or films which may be transformed by subsequent processing into product films exhibiting such ferroelectric, semiconductor or superconductor properties.
  • SBT films may initially be deposited with paraelectric properties, and subsequently be subjected to annealing to produce ferroelectric product SBT films.
  • the preferred mononuclear bismuth precursor of the present invention has been found to afford unexpected advantages in the CVD process, which in turn overcome the deficiencies associated with prior art usage of triphenyl bismuth, which has been the prior art's "standard” precursor for bismuth in CVD applications.
  • triphenyl bismuth precursor The deficiencies associated with the triphenyl bismuth precursor are significant.
  • the use of triphenyl bismuth as a bismuth precursor in standard solvent solutions such as 8:2:1 tetrahydrofuran/isopropanol/tetraglyme requires temperatures above 470°C to achieve acceptable Bi 2 O 3 deposition rates. It is desirable, however, to minimize deposition temperatures, since migration of bismuth and Bi 2 O 3 into the bottom electrode and into the substrate of ferroelectric capacitor structures increases with increasing temperature, leading to loss of bismuth in the ferroelectric film.
  • Such migration also presents a potential for bismuth contamination in deeper parts of the device structure, as well as significant instability of the plug structure of the ferroelectric capacitor and any barrier between the plug and the bottom electrode relative to oxidation thereof above 500°C.
  • the mononuclear ⁇ -diketonate bismuth precursor used in the process of the present invention permits deposition at acceptable rates at temperatures below 450°C down to temperatures as low as 300°C or less.
  • Films formed from ⁇ -diketonate precursors in accordance with the present invention have a much better conformality and morphology than those achieved using triphenyl bismuth as a precursor.
  • the triphenyl bismuth precursor of the prior art presents a functional mismatch with the Sr and Ta precursors used in the CVD process.
  • the deposition rate for SrO and Ta 2 O 5 is high at low pressures (e.g., 133 Pa (1 torr)), but in contrast the Bi 2 O 3 deposition rate is low.
  • Bi 2 O 3 deposition rates from the triphenyl bismuth precursor are high, while the SrO and Ta 2 O 5 deposition rates are low.
  • This opposedly mismatching character results in a very small "process window" for adequate operability for the CVD process.
  • the mononuclear ( ⁇ -diketonate) bismuth precursor of the present invention is well matched with the strontium and tantalum precursors, and when such bismuth source is used, all of the precursors have a high deposition rate at low pressures on the order of 1 torr.
  • the well-matched character of the mononuclear ( ⁇ -diketonate) bismuth precursor permits a wide process window to be utilized, for highly flexible processing in the formation of SBT films.
  • the Bi 2 O 3 deposition rate is more stable, because the precursor is less parameter-sensitive (e.g., oxygen-sensitive) and less substrate-sensitive.
  • the precursor is less parameter-sensitive (e.g., oxygen-sensitive) and less substrate-sensitive.
  • triphenyl bismuth deposition is very sensitive to process parameters such as pressure, gas flow, oxygen concentration, etc. In consequence, a constant film growth and time-independent film composition are more closely approached when using a mononuclear ( ⁇ -diketonate) bismuth composition as the precursor material.
  • mononuclear ( ⁇ -diketonate) bismuth precursors lower sensitivity is achieved in relation to process parameters as well as in relation to the character of the bottom electrode.
  • run-to-run reproducibility and uniformity within a wafer are excellent when such mononuclear ( ⁇ -diketonate) bismuth complex is employed as the precursor in the CVD process.
  • the SBT films formed by the CVD process of the present invention may be utilized to form a wide variety of structures and devices.
  • An illustrative device is shown in Figure 1.
  • the ferroelectric memory storage cell 10 is shown schematically as comprising a thin ferroelectric material layer 12 between plates 14 and 16 of a capacitor. Such capacitor is connected to the transistor 18 to form the storage cell, with the transistor being joined to a bit-line element 20 and to a word-line element 22, as shown.
  • FIG. 2 is a schematic representation of a stacked capacitor and transistor assembly illustrating how the SBT material can be integrated in a storage cell.
  • the capacitor 30 comprises a top electrode 32, and bottom electrode 34 on which is disposed a thin film ferroelectric material layer 36, as shown.
  • the bottom electrode 34 is connected by plug 38 to the drain 40 of the transistor.
  • the plug may be made of any suitable material, as for example from polysilicon or tungsten.
  • the transistor comprises gate 42 and a source 44.
  • FIG. 3 is a graph of film thickness in nanometers, as a function of time,-in minutes, for the growth of an SBT film having the composition Sr:18%, Bi:45% and Ta:37%.
  • the discussion herein is largely directed to end use applications involving the formation of SBT films, the invention is not thus limited, and the chemical vapor deposition process of the present invention contemplates the deposition of bismuth from a bismuth precursor, e.g., an anhydrous mononuclear ( ⁇ -diketonate) bismuth complex, optionally in combination with other metals from their respective precursors, to provide for deposition of bismuth per se as well as deposition of numerous other bismuth-containing metal or metal oxide films.
  • a bismuth precursor e.g., an anhydrous mononuclear ( ⁇ -diketonate) bismuth complex
  • Metal species which may be deposited on a substrate with bismuth deposited from the ( ⁇ -diketonate) bismuth precursor include for example potassium, calcium, strontium, barium, lead, iron, aluminum, scandium, yttrium, titanium, niobium, tantalum, tungsten, molybdenum, and lanthanide series metals including La, Ce, Pr, Ho, Eu, and Yb.
  • the CVD process employing the bismuth precursor in accordance with the present invention may be utilized for formation of SrBi 2 Ta 2 O 9 , SrBi 2 Ta 2-x Nb x O 9 wherein x is a number between 0 and 2, SrBi 2 Nb 2 O 9 , Sr 1-x Ba x Bi 2 Ta 2-y Nb y O 9 wherein x is a number between 0 and 1 inclusive, and y is a number between 0 and 2 inclusive, Sr 1-x Ca x Bi 2 Ta 2-y Nb y O 9 wherein x is a number between 0 and 1 inclusive and y is a number between 0 and 2 inclusive, Sr 1-x Pb x Bi z Ta 2-y Nb y O 9 wherein x is a number between 0 and 1 inclusive and y is a number between 0 and 2 inclusive, Sr 1-x-y-z Ba x Ca y Pb z Bi 2 Ta 2-p Nb p O 9 wherein x is a number between
  • Bi-containing oxide films may also be formed with substitution of one or more of the metal elements therein by a metal from the lanthanide series (e.g., La, Ce, Ho, Pr, Eu, Yb) or by doping of the film with a metal from the lanthanide series.
  • a metal from the lanthanide series e.g., La, Ce, Ho, Pr, Eu, Yb
  • doping of the film with a metal from the lanthanide series e.g., La, Ce, Ho, Pr, Eu, Yb
  • Bismuth titanate and related materials may also be formed by CVD using a ( ⁇ -diketonate) bismuth precursor in accordance with the present invention, to form a film having a composition according to one of the following metal oxide formulae: Bi 4 Ti 3 O 12 PrBi 3 Ti 3 O 12 HoBi 3 Ti 3 O 12 LaBi 3 Ti 3 O 12 Bi 3 TiTaO 9 Bi 3 TiNbO 9 SrBi 4 Ti 4 O 15 CaBiTi 4 O 15 BaBi 4 Ti 4 O 15 PbBi 4 Ti 4 O 15 Sr 1-x-y-z Ca x Ba y Pb z Bi 4 Ti 4 O 15 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1) Sr 2 Bi 4 Ti 5 O 18 Ca 2 Bi 4 Ti 5 O 18 Ba 2 Bi 4 Ti 5 O 18 Pb 2 Bi 4 Ti 5 O 18 Sr 2-x-y-z Ca x Ba y Pb z Bi 4 Ti 5 O 18 (0 ⁇ x ⁇ 2,
  • the various precursors employed in the CVD process of the present invention may be used in adducted form.
  • examples include ( ⁇ -diketonate) strontium adducts wherein the adduct ligand may be a polyether (e.g., R-(CH 2 CH 2 O) n -R' wherein n is a number between 2 and 6 inclusive, and each of R and R' are independently selected from H and alkyl), or a polyamine adduct, e.g., R-(CH 2 CH 2 NR") n -R' wherein n is a number between 2 and 6 inclusive, and each of R, R' and R" are independently selected from hydrogen and alkyl.
  • adduct ligand may be a polyether (e.g., R-(CH 2 CH 2 O) n -R' wherein n is a number between 2 and 6 inclusive, and each of R and R' are independently selected from H and alkyl)
  • a polyether e
  • Bismuth- and tantalum-containing films may be formed by a CVD process in accordance with the present invention, wherein the tantalum precursor has the general formula Ta(OR) 5-n (X) n and wherein R is C 1 - C 5 alkyl, X is ⁇ -diketonate, with n being an integer of 1 to 5 inclusive. Tantalum precursors of such type are more fully described in U.S. Patent 5,677,002 issued October 14, 1997 in the names of Peter S. Kirlin, et al.
  • X in such tantalum precursor may be 2,2,6,6-tetramethylheptane-3,5-dionate, or as abbreviated "thd.”
  • a preferred tantalum precursor of the foregoing general formula is Ta(OiPr) 4 (thd).
  • the various precursors employed in the broad practice of the invention to form bismuth-containing films may employ liquid delivery techniques wherein the precursor is dissolved in a suitable solvent, and the resulting liquid precursor solution is vaporized to form precursor vapor for contacting with the substrate in the CVD reactor.
  • Such liquid delivery technique may involve mixing of all, or more than one, but less than all of the precursors in a common solvent for concurrent vaporization, e.g., as a liquid multicomponent precursor solution which is formed and then vaporized to provide the multicomponent precursor vapor for flow to the CVD reactor.
  • multiple vaporizers may be employed, with separate precursors being delivered by liquid delivery to respective vaporizers where they are independently flash vaporized and the resulting vapor is thereafter mixed with vapor from another vaporizer unit, and with the joined vapor stream then being flowed to the CVD reactor.
  • the precursors employed in the broad practice of the present invention may be used with any suitable solvents which are compatible with the precursors dissolved therein and which do not preclude the CVD process from being carried out to produce the desired film.
  • suitable solvents include hydrocarbon solvents, including aliphatic, cycloaliphatic and aromatic hydrocarbons as well as substituted hydrocarbons, e.g., alcohols, ethers, esters, amines, ketones, and aldehydes.
  • the solvent may be employed as single species medium for the precursor, or solvent mixtures may be employed.
  • solvent mixtures may be employed as an illustrative example of multicomponent solvent mixtures.
  • an 8:2:1 by volume mixture of tetrahydrofuran, isopropanol and tetraglyme may be utilized.
  • Similar solvent mixtures utilizing, in place of the aforementioned tetraglyme component, a polyamine, may likewise be employed.
  • Hydrocarbon solvents having a carbon number greater than 7 may be employed, such as octane, nonane, decane, undecane, dodecane, tridecane or tetradecane, or mixture thereof.
  • the CVD process of the present invention contemplates using various permutations of solvents and specific precursor species, including the provision of all precursors in a single solution as a "cocktail" mixture for liquid delivery vaporization and chemical vapor deposition, as well as utilizing single component, binary, ternary and other multicomponent solvent solutions.
  • Single precursor solutions may be separately formulated and separately delivered to the liquid delivery system so that the precursor solutions are mixed before vaporization, or separate vaporizers may be employed for certain ones of multiple precursor solutions, with the resulting vapor being joined for passage to the CVD reactor.
  • the vaporization of the liquid precursors may be carried out at any suitable process conditions, with lower temperatures on the order of 170-230°C being most preferred.
  • the CVD process itself may be carried out in any suitable manner, optionally enhanced by physical or chemical techniques (e.g., plasma-assisted CVD, photoactivation CVD, etc.).
  • physical or chemical techniques e.g., plasma-assisted CVD, photoactivation CVD, etc.
  • the CVD reactor may be maintained at any suitable process conditions, including suitable substrate temperatures for deposition, and gaseous oxidizer may be admixed to the precursor vapor either before or after entering the CVD reactor.
  • the CVD reactor may be maintained at any suitable pressure level during the deposition process, e.g., a pressure in the range of .133-101,080 Pa (0.001-760 torr). Most preferably, the pressure is in a range of from about 13.3 (0.1) to about 1330 Pa (10 torr).
  • the deposition temperature for the deposition of bismuth may be effected at temperatures below about 450°C, it being recognized that the specific temperatures which are advantageously employed in a given end use application may be readily determinable by ordinary skilled artisans without undue experimentation.
  • Flow rate of precursor vapor and any added carrier gas may be at any suitable volumetric flow rate, e.g., 1-16,000 standard cubic centimeters per minute (sccm).
  • an anhydrous mononuclear ( ⁇ -diketonate) bismuth precursor is deposited on a substrate at a temperature below about 600°C to form a non-ferroelectric bismuth ceramic film, which then is transformed to the ferroelectric form by transformation steps which typically comprise one or more annealing steps.
  • the annealing may be carried out at temperatures on the order of about 600-820°C.
  • the process of the invention is well-suited for the formation of bismuth-containing ceramic films which can be transformed into ferroelectric films with a layered pseudo-perovskite structure (Aurivillius phase) of the following general formula: (Bi 2 O 2 ) 2+ (A m-1 B m O 3m+1 ) 2- , wherein
  • the bismuth precursor preferably is anhydrous mononuclear tris ( ⁇ -diketonate) bismuth.
  • the ⁇ -diketonate ligand may for example comprise any of the illustrative species set out below.
  • the CVD process of the present invention for forming bismuth-containing thin films may be employed in the manufacture of a wide variety of thin film products, including ferroelectric capacitors, ferroelectric transistors, e.g., field effect transistors of such type, ferroelectric random access memories, chip cards, and integrated device structures, utilizing bismuth-containing thin films such as SBT and SBT derivatives, e.g., SrBi 2 (Nb,Ta) 2 O 7 (SBNT), or alternatively Bi 4 Ti 3 O 12 and derivatives thereof.
  • SBT and SBT derivatives e.g., SrBi 2 (Nb,Ta) 2 O 7 (SBNT)
  • Ferroelectric thin film capacitors may be fabricated utilizing a bismuth-containing ferroelectric thin film material, in conjunction with any suitable electrode structures.
  • such capacitor may utilize a bottom electrode formed of a material such as Pt, Pd, Au, Ir, Rh, conducting metal oxides such as IrO x , RhO x , RuO x , OsO x , ReO x , WO x , wherein x is between 0 and 2, conducting metal nitrides such as TiN x , ZrN x , wherein x is between 0 and 1.1 or W x ,TaN x , wherein x is from 0 to 1.7, or a superconducting oxide (e.g., YBa 2 Cu 2 O 7-x or Bi 2 Sr 2 Ca 2 Cu 3 O 10 ).
  • a superconducting oxide e.g., YBa 2 Cu 2 O 7-x or Bi 2 Sr 2 Ca 2 Cu 3 O 10
  • Additional layers may be interposed between the bottom electrode and the ferroelectric thin film in the capacitor structure, such as seed layers, conducting layers, paraelectric layers or dielectric layers.
  • Such a capacitor may have a top electrode of platinum or other suitable material.
  • the ferroelectric capacitor may be employed as a stack capacitor interconnected by a plug with a transistor on a substrate, as shown in Figure 2 hereof, optionally with a further barrier layer (not shown in Figure 2) between the bottom electrode 34 and the plug 38.
  • the plug may be formed of polysilicon or tungsten, and may as shown be fabricated on the drain of a MOSFET, and the optional additional layers between the bottom electrode and plug (not shown in Figure 2) may constitute adhesion layers, diffusion barrier layers, or the like.
  • the specific CVD process methodology used to form the bismuth-containing film may be widely varied, and may for example comprise the steps of positioning a substrate in the CVD reactor chamber, heating the substrate up to a deposition temperature, flushing the substrate with a mixture of inert gas and oxidizer, delivering precursor vapor mixed with inert carrier gas and, if required, an oxidizer, exposing the substrate to such precursor vapor following which precursor vapor flow is discontinued and the substrate is flushed with a mixture of inert gas and, if required, an oxidizer, with the substrate then being cooled and removed from the chamber, or removed for such cooling.
  • the substrate may be pretreated in the CVD reactor prior to deposition by exposing the substrate to vapors of a predetermined composition and/or annealing.
  • the CVD step may be carried out in a single continuous process, or in discrete steps, e.g., with intermediate removal of the substrate from the CVD chamber for performing other processing on the substrate, following which the substrate is reintroduced to the CVD chamber to continue CVD of the bismuth-containing material.
  • the CVD process may be carried out with variation of process conditions (e.g., temperature, pressure, flow rates and gas phase composition) over the period of the process, or such process conditions may be maintained at stable set point values during the process.
  • the bismuth-containing film may be annealed prior to deposition of a top electrode thereover, followed by additional annealing, or such annealing may simply be carried out after the top electrode has been formed on the ferroelectric thin film.
  • the annealing step generally may be carried out at temperatures on the order of about 600 to about 820°C.
  • SBT is deposited on a substrate utilizing Sr(thd) 2 (tetraglyme) as the Sr precursor, mononuclear Bi(thd) 3 as the bismuth precursor and Ta(OiPr) 4 (thd) as the tantalum precursor.
  • the precursors are each dissolved in a solvent mixture and stored separately in three respective reservoirs.
  • the solvent for each precursor is a 8:2:1 by volume mixture of tetrahydrofuran:isopropanol:tetraglyme.
  • Molar concentrations of the precursors are 0.4 moles/liter(molar) for the tantalum precursor, 0.25 moles/liter(molar) for the bismuth precursor, and 0.15 moles/liter(molar) for the strontium precursor.
  • the three precursor solutions Prior to delivery, the three precursor solutions are mixed in a liquid delivery system to provide the desired precursor composition.
  • the precursor mix is delivered by a pump, preferably at a volume entry flow rate in the range of from about 0.05 to about 0.25 milliliters per minute, to a vaporizer comprising two chambers separated by a frit.
  • the vaporizer is maintained at a temperature in the range from about 170 to about 200°C.
  • the precursor solution is introduced to the hot surface of the frit to vaporize the solvent and precursors via flash vaporization.
  • Argon carrier gas preferably at a flow rate of from about 200 to about 600 sccm, is flowed through the vaporization unit to transport the precursor vapor to a showerhead disperser assembly where the precursor vapor is mixed with additional argon and with oxygen as an oxidizer.
  • the resulting mixture of precursor vapor, carrier gas and oxidizer enters the CVD chamber and is directed at the hot substrate, whose temperature is maintained by a resistively heated chuck.
  • the gases are exhausted from the CVD chamber through a cold trap into a vacuum pump with high conductance. Pressure in the system is maintained by a throttle valve and by adjustment of total gas flow. All reactor walls as well as the showerhead and connecting lines (vaporizer-showerhead, chamber-cold trap) are heated to a temperature in the range of 170-260°C.
  • the deposition is carried out on a substrate, e.g., a Pt/Ti/SiO 2 /Si wafer wherein the platinum thickness is 100 nanometers and the titanium thickness is 10 nanometers, introduced to the CVD chamber through a load lock and put on the hot chuck.
  • a substrate e.g., a Pt/Ti/SiO 2 /Si wafer wherein the platinum thickness is 100 nanometers and the titanium thickness is 10 nanometers
  • the wafer is heated up to process temperature, then oxygen gas flow is turned on to establish the oxygen/argon ratio at a desired value. Following establishment of such ratio, the precursor gas is flowed into the chamber and deposition is carried out, following which the precursor vapor flow is turned off and the chamber is flushed with the argon/oxygen mixture.
  • the wafer then is removed from the chamber through the load lock.
  • the as-deposited film produced by the foregoing process is specular and has a high density.
  • SEM images show grains having a size on the order of 80nm.
  • the x-ray diffraction spectrum of the as-deposited film reveals two peaks which can be assigned to an oriented fluorite structure as shown in Figure 4.
  • Such oriented fluorite structure can be transformed to a desired Aurivillius phase by post-deposition annealing.
  • FIG. 5 shows an atomic force microscope (AFM) map of a sample produced by a process similar to that described above, wherein the SBT film is deposited at 385°C and has a composition of 18.6 atomic % Sr, 43.4 atomic % Bi and 38.0 atomic % Ta, with a film thickness of 216 nanometers. The mean roughness of such surface is 6.8 nanometers.
  • AFM atomic force microscope
  • An SBT film was deposited on a platinum substrate by a process of the general type described in Example II.
  • the Pt layer was approximately the same thickness as the SBT layer, as is shown in the TEM bright field image of the as-deposited film in Figure 7, the inset portion of which is an electron diffraction pattern evidencing the amorphous character of most of the SBT film.
  • amorphous layer is converted to the Aurivillius SBT phase as shown in Figure 8, which is a Cu K-alpha x-ray diffraction spectrum of a sample deposited at 385°C and annealed at 800°C.
  • a solution containing 7 mol-% Sr(thd) 2 (pentamethyldiethylenetriamine), 55 mol-% Bi(thd) 3 , and 38% Ta(OiPr) 4 (thd) in a 5:4:1 octane:decane:pentamethyldiethylenetriamine solvent mixture is metered at a flow rate of 0.2 milliliters per minute to the liquid delivery system, where it is flash vaporized at 190°C and then transported to the CVD chamber in 400 sccm argon.
  • This precursor-containing vapor stream is mixed with 1100 sccm oxygen and an additional 100 sccm argon for a combined 7:3 oxygen:argon ratio as it passes through a showerhead disperser into the CVD chamber which is maintained at 133 Pa (1 torr).
  • Decomposition occurs on a substrate heated to a surface temperature of 385°C.
  • the substrate comprises a 0.5 micrometer line width plasma deposited SiO 2 (TEOS) structure covered with platinum.
  • Figure 9 is a micrograph showing the conformality of the SBT film on this structure.
  • the minimum SBT thickness achieved is greater than 90% of the maximum thickness (side wall thickness to top surface thickness), satisfying the requirements for microelectronic device fabrication.
  • the low temperature and amorphous nature of the deposition permits the conformal coating of the substrate. Under such conditions, the composition varies less than 5% relative (0.5% being the precision of the x-ray fluorescence method employed) between 30 millimeter spots on a 150 millimeter wafer.
  • An as-deposited film formed by a process similar to that of Example II was annealed at 800°C for one hour in an oxygen gas stream (2.5slm). Top electrodes then were deposited by deposition of 200 micrometer thickness platinum through a shadow mask. The average size of the top electrodes was between 4 x 10 -4 and 2 x 10 -3 cm 2 . After the deposition of the top electrodes the capacitors were annealed again at 800°C for 15 minutes in a 2.5 slm oxygen flow.
  • a solution containing 18 atomic % Sr(thd) 2 (pentamethyldiethylenetriamine), 40 atomic % Bi(thd) 3 and 42 atomic % Ta(OiPr) 4 (thd) in a solvent mixture (5:4:1 octane:decane:pentamethyldiethylenetriamine) is metered to the process where it is flash vaporized at 190°C. and then flowed to the deposition reactor chamber in 400 sccm argon.
  • the vapor is mixed with 6000 sccm O 2 and additional 3600 sccm argon for a combined 6:4 oxygen: argon ratio.
  • the resulting combined stream is passed through a showerhead disperser into the reactor chamber which is maintained at 9 torr.
  • Decomposition occurs on a substrate heated to a surface temperature of 385°C. Under these conditions, the evidence of fluorite phase by x-ray diffraction, and can be converted to the Aurivilius phase without an intermediate fluorite phase.
  • Runs 1-3 had a low growth rate and showed a fluorite phase in the as-deposited film. Electrical properties, annealing behavior and surface morphology of these films were similar to those deposited at 133 Pa (1 torr) and described in the earlier examples herein.
  • Run 4 had a significantly higher deposition rate and showed only amorphous material in the as-deposited film, as is apparent from the Figure 11 x-ray diffraction spectrum of the amorphous SBT film produced in Run 4. The results of Run 4 are reproducible.
  • both deposition temperature and growth rate mainly determine whether an as-deposited film is amorphous or partly crystallized.
  • increasing the growth rate and decreasing the temperature will lower the migration of Bi species at the surface.
  • the Bi migration is lowered or - in the best case - suppressed, there will be less tendency for a crystallization to occur during the deposition.
  • the film is amorphous. It therefore is possible to deposit amorphous films even at higher temperatures such as 430°C or 450°C if the growth rate is high enough.
  • Bi aryl precursors it may be more difficult to obtain the high growth rates at the temperatures discussed above, but this difficulty may be surmounted by using means such as RF plasma, photoactivation or process additives such as alcohols to achieve sufficient deposition rates for Bi 2 O 3 at lower temperatures.
  • Other Bi precursors such as Bi carboxylates, Bi alkoxides and Bi amides have low deposition temperatures and therefore are potentially usefully employed in the formation of amorphous SBT films.
  • the amorphous films of the invention shown superior properties to all other deposited films of the prior art, for the following reasons.
  • Figure 12 is an x-ray diffraction spectrum of an Aurivillius phase film, formed from an amorphous as-deposited SBT film deposited at 380°C, and subjected to annealing at 750°C for 5 minutes to form the Aurivillius phase.
  • Figure 13 is an x-ray diffraction spectrum of another Aurivillius phase SBT film deposited in accordance with the present invention at 380°C, and then annealed at 700°C for 10 minutes to form the Aurivillius phase with complete phase transformation.
  • the ferroelectric properties of the ferroannealed films are superior to those generated from crystalline as-deposited films.
  • the 2P r values were significantly increased and at lower annealing temperatures high 2P r values are possible.
  • the amorphous films are much smoother than the crystalline films.
  • an amorphous SBT CVD film may be formed at a low deposition temperature.
  • This amorphous CVD film may be converted directly to the Aurivillius SBT phase, or converted through an intermediate fluorite phase to the Aurivillius SBT phase.
  • the deposited film may also be formed as a mixed amorphous and fluorite phase film which is then converted to the Aurivillius SBT phase.
  • the foregoing results also show that a highly conformal SBT film may be readily formed by the low temperature CVD process of the invention.
  • the chemical vapor deposition process of the present invention is usefully employed for forming bismuth-containing films on substrates for applications such as fabricating non-volatile memory devices.
  • the process of the invention may be employed to deposit bismuth oxide materials such as SrBi 2 Ta 2 O 9 , Bi 4 Ti 3 O 12 , and the like, for forming ferroelectric thin films for ferroelectric memory devices.
  • Memory devices may be formed in which a ferroelectric capacitor is connected to a transistor to form a storage cell structure, to provide ferroelectric memory devices that retain stored information in the event of termination of the associated power supply, and that do not require refresh cycles.

Claims (31)

  1. Verfahren zum Abscheiden eines aus Wismut bestehenden, eines wismuthaltigen oder eines Strontium-Wismut-Tantalat-Films auf ein Substrat ausgehend von einem Precursor, umfassend folgende Verfahrensschritte: Verdampfen eines Wismut-β-diketonat Precursors zur Bildung eines verdampften Precursors und In-Kontakt-Bringen des verdampften Precursors mit dem Substrat zum Abscheiden von Wismut oder eines wismuthaltigen Films auf dieses Substrat, dadurch gekennzeichnet, dass der Wismut-β-diketonat Precursor ein wasserfreies mononukleares Wismut-β-diketonat aufweist und der Schritt des In-Kontakt-Bringens des verdampften Precursors mit dem Substrat zum Abscheiden des aus Wismut bestehenden oder wismuthaltigen Films auf das Substrat bei einer Temperatur unterhalb von 450 °C durchgeführt wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Wismut-β-diketonat Precursor eine Wismutzusammensetzung nach der Formel

            BiAxBy

    aufweist,
    dadurch gekennzeichnet, dass:
    A = β-diketonat ;
    B = ein weiterer Ligand, der mit Bi und A aus der Zusammensetzung kompatibel ist;
    x = 1, 2 oder 3; und
    y = 3-x.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass der Wismut-β-diketonat Precursor ein wasserfreies mononukleares Wismut-β-diketonat bei einer Temperatur von 385 °C oder darunter aufweist.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der wismuthaltige Film SrBi2Ta2O9 aufweist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Wismut-β-diketonat Precursor wasserfreies mononukleares Tris(2,2,6,6-tetramethyl-3,5-heptandionato)-wismut aufweist.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Verdampfen des Wismut-β-diketonat Precursors zur Bildung des verdampften Precursors den flüssigen Zufluss und die Entspannungsverdampfung des Wismut-β-diketonat Precursors aufweist.
  7. CVD-Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Abscheidungstemperatur 380 °C nicht überschreitet.
  8. CVD-Verfahren nach einem der Ansprüche 1 oder 7, dadurch gekennzeichnet, dass der Wismutprecursor wasserfreies mononukleares Bi Tris(2,2,6,6-tetramethyl-3,5-heptandionato) ist.
  9. CVD-Verfahren nach einem der Ansprüche 1 bis 8 zum Bilden eines wismuthaltigen Films, der in einen ferroelektrischen Film mit einer geschichteten Pseudo-Perovskitstruktur der allgemeinen Formel

            (Bi2O2)2+(Am-1BmO3m+1)2-

    umgewandelt werden kann;
    wobei
    A = Bi3+, L3+, L2+, Ca2+, Sr2+, Ba2+, Pb2+, Na+;
    B = Fe3+, Al3+, Sc3+, Y3+, L3+, L4+, Ti4+, Nb5+, Ta5+, W6+, Mo6+;
    L = ein Lanthanidmetall ; und
    m= 1, 2, 3, 4, 5.
  10. CVD-Verfahren nach einem der Ansprüche 1 bis 8 zum Bilden eines wismuthaltigen Films aus einem Material ausgewählt aus der Gruppe bestehend aus:

            SrBi2Ta2O9

            SrBi2Ta2-xNbxO9 (0 < x < 2)

            SrBi2Nb2O9

            Sr1-xBaxBi2Ta2-yNbyO9 (0 ≤ x ≤ 1, 0 ≤ y ≤ 2)

            Sr1-xCaxBi2Ta2-yNbyO9 (0 ≤ x ≤ 1, 0 ≤ y ≤ 2)

            Sr1-xPbxBi2Ta2-yNbyO9 (0 ≤ x ≤ 1, 0 ≤ y ≤ 2)

            Sr1-x-y-zBaxCayPb2Bi2Ta2-pNbpO9 (0 ≤ x ≤ 1,0 ≤ y ≤ 1,0 ≤ z ≤ 1,0 ≤ p ≤ 2)

  11. CVD-Verfahren nach einem der Ansprüche 1 bis 8 zum Abscheiden eines Wismut-Titanat-Materials ausgewählt aus der Gruppe bestehend aus

            Bi4Ti3O12

            PrBi3Ti3O12

            HoBi3Ti3O12

            La B13Ti3O12

            Bi3TiTaO9

            Bi3TiNbO9

            SrBi4Ti4O15

            CaBi4Ti4O15

            BaBi4Ti4O15

            PbBi4Ti4O15

            Sr1-x-y-zCaxBayPb2Bi4Ti4O15 (0 ≤ x ≤ 1,0 ≤ y ≤ 1,0 ≤ z ≤ 1)

            Sr2Bi4Ti5O18

            Ca2Bi4Ti5O18

            Ba2Bi4Ti5O18

            Pb2Bi4Ti5O18

            Sr2-x-y-zCaxBayPb2Bi4Ti5O18 (0 ≤ x ≤ 2,0 ≤ y ≤ 2,0 ≤ z ≤ 2)

            SrBi5Ti4FeO18

            CaBi5Ti4FeO18

            BaBi5Ti4FeO18

            PbBi5Ti4FeO18

            Sr1-x-y-zCaxBayPb2Bi5Ti4 FeO18 (0 ≤ x ≤ 1,0 ≤ y ≤ 1,0 ≤ z ≤ 1)

            Bi5Ti3FeO15

            LaBi4Ti3FeO15

            PrBi4Ti3FeO15

            Bi6Ti3FeO18

            Bi9Ti3Fe5O27

  12. CVD-Verfahren nach einem der Ansprüche 1 bis 8 zum Abscheiden einer Wismutphase ausgewählt aus der Gruppe bestehend aus

            Bi2WO6

            BiMO3 (M = Fe, Mn)

            Ba2BiMO6 (M = V, Nb, Ta)

            Pb2BiMO6 (M = V, Nb, Ta)

            Ba3Bi2MO9 (M = Mo, W)

            Pb3Bi2MO9 (M = Mo, W)

            Ba6BiMO18 (M = Mo, W)

            Pb6BiMO18 (M = Mo, W)

            KBiTi2O6

            K2BiNb5O15

  13. CVD-Verfahren nach einem der Ansprüche 1 bis 12, ferner umfassend das Abscheiden von Sr ausgehend von einem Precursor ausgewählt aus der Gruppe bestehend aus Sr(thd)2 und Sr(thd)2-Addukten.
  14. CVD-Verfahren nach Anspruch 13, wobei der Sr-Addukt ausgewählt ist aus der Gruppe bestehend aus Tetraglym (=MeO-(CH2CH2O)4-Me), Triglym (=MeO-(CH2CH2O)3-Me), N,N,N',N",N"-Pentamethyldiethylentriamin (=Me2N-(CH2CH2NMe)2-Me) und N,N,N',N",N"',N"'-Hexamethyltriethylentetramin (=Me2N-(CH2CH2NMe)3-Me).
  15. CVD-Verfahren nach einem der Ansprüche 1 bis 14, ferner umfassend das Abscheiden von Tantal ausgehend von einem Ta-Precursor der allgemeinen Formel Ta(OR)5-n(X)n, dadurch gekennzeichnet, dass R = Me, Et, N-Pr, I-Pr, N-Bu, I-Bu, T-Bu, N-pentyl oder I-pentyl, X = β-Diketonat und N = 1, 2, 3, 4, oder 5.
  16. CVD-Verfahren nach Anspruch 15, wobei Ta(OiPr)4(thd) als Ta-Precursor verwendet wird, dadurch gekennzeichnet, dass thd = 2,2,6,6,Tetramethylheptan-3,5-dionat.
  17. CVD-Verfahren nach einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, dass der Precursor in einem Lösemittel umfassend ein aliphatisches, ein cycloaliphatisches oder ein aromatisches Kohlenwasserstoff-Lösemittel vorliegt.
  18. CVD-Verfahren nach Anspruch 17 unter Verwendung einer Mischung aus THF, iPrOH und Tetraglym als Precursor-Lösemittel.
  19. CVD-Verfahren nach Anspruch 17 oder 18 unter Verwendung einer Mischung aus THF, iPrOH und eines Polyamins als Precursor-Lösemittel.
  20. CVD-Verfahren nach einem der Ansprüche 17 bis 19 unter Verwendung eines Kohlenwasserstoff-Lösemittels umfassend ein Alkan mit einer Kohlenstoffzahl größer als sieben als Precursor-Lösemittel.
  21. CVD-Verfahren nach einem der Ansprüche 17 bis 20 unter Verwendung von Oktan, Dekan und Pentamethyldiethylentriamin als Precursor-Lösemittel.
  22. CVD-Verfahren nach einem der Ansprüche 1 bis 21, dadurch gekennzeichnet, dass der Precursor bei einer Temperatur im Bereich von 170 bis 230 °C verdampft wird.
  23. CVD-Verfahren nach einem der Ansprüche 1 bis 22, dadurch gekennzeichnet, dass ein wismuthaltiger Film über eine Bodenelektrode aufgebracht wird, welche aus einem Material gebildet ist, das ausgewählt ist aus der Gruppe bestehend aus den Metallen Pt, Pd, Au, Ir, Rh und deren Legierungen, leitenden Metalloxyden IrOx, RhOx, RuOx (0 < x < 2) und aus Mischungen derselben mit einem oder mehreren der besagten Metalle, leitenden Metallnitriden TiNx, ZrNx (0 < x < 1,1), Wx, TaNx (0 < x < 1,7) und supraleitenden Oxyden ausgewählt aus der Gruppe bestehend aus YBa2Cu2O7-x und Bi2Sr2Ca2Cu3O10.
  24. CVD-Verfahren nach einem der Ansprüche 1 bis 23 zur Bildung eines wismuthaltigen ferroelektrischen Films in einer Speicherzellenstruktur, die zwischen der Bodenelektrode und dem ferroelektrischen dünnen Film eine Schicht aufweist, ausgewählt aus der Gruppe bestehend aus Keimschichten, leitenden Schichten, paraelektrischen Schichten und dielektrischen Schichten.
  25. CVD-Verfahren nach einem der Ansprüche 1 bis 24 mit einem Abscheidedruck von 0,133 bis 101.080 Pa (0,001 bis 760 Torr).
  26. CVD-Verfahren nach Anspruch 27 mit einem Abscheidedruck von 13,3 bis 1.333 Pa (0,1 bis 10 Torr).
  27. CVD-Verfahren nach einem der Ansprüche 1 bis 26 mit einem Gesamtgasfluss während der Abscheidung von 1 bis 16.000 sccm.
  28. CVD-Verfahren nach einem der Ansprüche 1 bis 27, dadurch gekennzeichnet, dass ein Oxidationsmittel mit dem Precursordampf vermischt wird und dass das Oxidationsmittel ausgewählt ist aus der Gruppe bestehend aus O2, Singulettsauerstoff, Ozon, NOx, wobei x = 1, 2 oder 3, Wasserstoffperoxid, Sauerstoffplasma, N2O und aus Mischungen derselben.
  29. CVD-Verfahren nach einem der Ansprüche 1 bis 28 umfassend die folgenden Verfahrensschritte:
    Einlegen des Substrats in eine CVD-Reaktionskammer,
    Erwärmen des Substrats auf die Abscheidungstemperatur,
    Spülen des Substrats mit einer Mischung aus einem Inertgas und wahlweise aus einem Oxidationsmittel,
    Zuführen des mit einem Inertgas und wahlweise mit einem Oxidationsmittel vermischten Precursordampfes,
    Aussetzen des Substrats dem Precursordampf,
    Unterbrechen des Flusses des Precursordampfes,
    Spülen des Substrats mit einer Mischung aus einem Inertgas und wahlweise aus einem Oxidationsmittel und Kühlen des Substrats.
  30. CVD-Verfahren nach Anspruch 29, ferner umfassend folgende Nachbehandlungsschritte:
    Entspannen des Films bei 600 bis 800 °C,
    Aufbringen einer oberen Elektrode auf den Film, und
    weiteres Entspannen des Films bei einer Temperatur im Bereich von 600 bis 800 °C.
  31. CVD-Verfahren nach Anspruch 29 oder 30 umfassend das Ändern der Verfahrensparameter ausgewählt aus der Gruppe bestehend aus Temperatur, Druck, Gasfluss und Gasphasenzusammensetzung während des Verfahrens.
EP98934193A 1997-06-26 1998-06-26 Niedrig temperatur cvd-verfahren zur herstellung von wismuth enthaltenden dünnen keramik-schichten zur verwendung in ferroelektrischen speicheranordnungen Expired - Lifetime EP0990059B1 (de)

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US5008197P 1997-06-26 1997-06-26
US50081P 1997-06-26
US08/975,087 US6303391B1 (en) 1997-06-26 1997-11-20 Low temperature chemical vapor deposition process for forming bismuth-containing ceramic films useful in ferroelectric memory devices
PCT/US1998/013470 WO1999000530A1 (en) 1997-06-26 1998-06-26 Low temperature chemical vapor deposition process for forming bismuth-containing ceramic thin films useful in ferroelectric memory devices
US975087 2001-10-09

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EP0990059A1 (de) 2000-04-05
JP2001521584A (ja) 2001-11-06
KR20010014219A (ko) 2001-02-26
WO1999000530A9 (en) 1999-04-22
EP0990059A4 (de) 2000-11-02
JP3723226B2 (ja) 2005-12-07
US6303391B1 (en) 2001-10-16
US20010041374A1 (en) 2001-11-15
DE69838502D1 (de) 2007-11-15
US6730523B2 (en) 2004-05-04
WO1999000530A1 (en) 1999-01-07
AU8377498A (en) 1999-01-19

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